Method for depositing film and oil-repellent substrate

ABSTRACT

The method for depositing a film of the present invention comprises the first film deposition step of depositing a first film  103  having hardness higher than hardness of a substrate  101  on a surface of the substrate  101 , the first irradiation step of irradiating particles having energy on the first film  103 , and the second film deposition step of depositing an oil-repellent film  105  on a surface of the first film  103  subjected to the first irradiation step. According to the present invention, a method for depositing a film enabling production of an oil-repellent substrate comprising an oil-repellent film having abrasion resistance of a practically sufficient level can be provided.

TECHNICAL FIELD

The present invention relates to a method for depositing a film and anoil-repellent substrate.

BACKGROUND ART

There is known an oil-repellent article prepared by coating scratcheshaving a depth of 10 to 400 nm on a surface of a substrate consisting ofglass, plastics, or the like so that the surface has fine streakyconvexes and concaves in a predetermined direction, and then coating anoil-repellent film having a predetermined composition on the surfacehaving the fine convexes and concaves (Patent document 1).

PRIOR ART REFERENCE Patent Document

-   Patent document 1: Japanese Patent Unexamined Publication (KOKAI)    No. 9-309745

SUMMARY OF THE INVENTION Object to be Achieved by the Invention

When oil components, such as fingerprint components, adhere to anoil-repellent film surface of an oil-repellent article of this type, theoil components are wiped off with wiping cloth or the like.

In an oil-repellent article formed by the method of Patent document 1,streaky scratches are coated in a predetermined direction with apredetermined depth on the surface of the substrate. Therefore, it has aproblem that when wiping cloth or the like is slid on the surface in adirection crossing the scratches to wipe off the oil components, theoil-repellent film coated as the outermost surface layer is easilyshaved off, and oil repellency of the oil-repellent film is eliminatedby such wear.

In particular, the traverse friction test of the oil-repellent articleformed by the method of Patent document 1 was performed with canvascloth under a condition that a small load of 0.1 kg/cm² was applied(refer to the paragraph [0038] of Patent document 1), and it cannot besaid that the oil-repellent film has practically sufficient abrasionresistance only with such a test.

An object of the present invention is to provide an oil-repellentsubstrate having an oil-repellent film showing practically sufficientabrasion resistance, and a method for depositing a film, which enablesproduction of such an oil-repellent substrate.

Means for Achieving the Object

The present invention achieves the aforementioned object with the meansfor achieving the object described below. The means for achieving theobject described below is explained with numerical notationscorresponding to those used in the drawings showing embodiments of thepresent invention. However, these notations are used only for making iteasier to understand the present invention, and are not intended tolimit the scope of the present invention.

The method for depositing a film of the present invention comprises thefirst film deposition step of depositing a first film (103) on a surfaceof a substrate (101) by using a dry process, the first irradiation step(postoperative irradiation) of irradiating particles having energy onthe first film (103), and the second film deposition step of depositinga second film (105) having oil repellency on a surface of the first film(103) subjected to the first irradiation step.

As the particles having energy used for the first irradiation step, forexample, particles having energy of accelerating voltage at 100 to 2000V, particles having energy of current density at 1 to 120 μA/cm², orparticles having energy of accelerating voltage at 100 to 2000 V andcurrent density at 1 to 120 μA/cm² can be used. In the first irradiationstep, the irradiation time of the particles having energy may be, forexample, 1 to 800 seconds, and the number of particles having energy tobe irradiated may be, for example, 1×10¹³ to 5×10¹⁷ particles/cm². Theparticles having energy used for the first irradiation step may consistof an ion beam containing at least argon (for example, ion beam ofargon, or ion beam of a mixed gas of oxygen and argon).

In the first film deposition step, the first film (103) can be depositedwith a thickness of 3 to 1000 nm. Further, in the first film depositionstep, the first film (103) can be deposited by the ion-assisteddeposition method using an ion beam, or can be deposited by repeating asputtering treatment and a plasma treatment. When the first filmdeposition step is performed by the ion-assisted deposition method, asthe ion beam used for this film deposition, for example, an ion beam ofaccelerating voltage at 100 to 2000 V, an ion beam of current density at1 to 120 μA/cm², or an ion beam of accelerating voltage at 100 to 2000 Vand current density at 1 to 120 μA/cm² can be used. In the first filmdeposition step, the irradiation time of the ion beam may be, forexample, 1 to 800 seconds, and the number of particles of the ion beamto be irradiated may be, for example, 1×10¹³ to 5×10¹⁷ particles/cm².The ion beam used for the first film deposition step may be an ion beamof oxygen, an ion beam of argon, or an ion beam of a mixed gas of oxygenand argon.

In advance of the first film deposition step, a second irradiation step(preoperative irradiation) for irradiating a surface of the substrate(101) with particles having energy may be performed. As the particleshaving energy used for the second irradiation step, for example,particles having energy of accelerating voltage at 100 to 2000 V,particles having energy of current density at 1 to 120 μA/cm², orparticles having energy of accelerating voltage at 100 to 2000 V andcurrent density at 1 to 120 μA/cm² can be used. In the secondirradiation step, the irradiation time of the particles having energymay be, for example, 60 to 1200 seconds, and the number of particleshaving energy to be irradiated may be, for example, 5×10¹⁴ to 5×10¹⁷particles/cm². The particles having energy used for the secondirradiation step may consist of an ion beam containing at least argon oroxygen (for example, ion beam of argon, ion beam of oxygen, or ion beamof a mixed gas of oxygen and argon).

In the oil-repellent substrate (100) of the present invention, the firstfilm (103) is coated on the surface of the substrate (101), the secondfilm (105) having oil repellency is coated on the surface of the firstfilm (103), and the first film (103) has the following surfacecharacteristics as measured by the methods defined in JIS-B0601: centerline average height (Ra): 0.1 to 1000 nm, 10-point average height (Rz):5 to 2000 nm, and maximum valley depth (Pv): 15 to 2000 nm.

The convexes observed on the surface of the first film (103) may existwith periodic intervals of 0.1 to 5000 nm. Even after the second film(105) is reciprocally rubbed with steel wool #0000 with a load of 1kg/cm² over 500 times, oily pen ink on the film can be wiped off. Thefirst film (103) may be composed of a material having hardness higherthan that of the substrate (101). The hardness is represented by a valueof pencil hardness measured by the method defined in JIS-K5600-5-4.Difference of the hardness values of the first film (103) and thesubstrate (101) is preferably two or more in terms of score of thepencil hardness measured by the method defined in JIS-K5600-5-4 (forexample, when the latter is 7H, the former is 9H or higher).

Effect of the Invention

According to the present invention, since particles having predeterminedenergy are irradiated on the predetermined first film that is depositedon the surface of the substrate (the first irradiation step),appropriate concaves are formed on the surface of the first filmsubjected to the irradiation. Therefore, the components constituting thesecond film having oil repellency (oil-repellent molecules), which aredeposited thereafter, can also adhere to the concaves of the first film.Abrasion resistance of the second film deposited on the surface of thefirst film can be thereby improved to a practically sufficient level.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a sectional view of an oil-repellent substrate according tothe first embodiment.

FIG. 2 is a sectional view of a film deposition system according to thesecond embodiment seen from the front, which enables production of theoil-repellent substrate of FIG. 1.

FIG. 3 is a sectional view of a film deposition system according to thethird embodiment seen from the front, which enables production of theoil-repellent substrate of FIG. 1.

FIG. 4 is a sectional view of an important part of the film depositionsystem of FIG. 3 seen from the side.

FIG. 5 is an enlarged explanatory view of a part of the film depositionsystem of FIG. 3 around the sputtering region.

FIG. 6 is an enlarged explanatory view of a part of the film depositionsystem of FIG. 3 around the plasma treatment region.

DESCRIPTION OF NUMERICAL NOTATIONS

100 . . . Oil-repellent substrate, 101 . . . substrate, 103 . . . firstfilm, 105 . . . oil-repellent film (second film), 1, 1 a . . . filmdeposition system, 2 . . . vacuum vessel, 30A . . . vapor depositionregion, 34, 36 . . . vapor deposition source, 34 a, 36 a, 38 a . . .shutter, 34 b, 36 b . . . crucible, 34 c . . . electron gun, 34 d . . .electron gun power supply, 38 . . . ion gun, 38 b . . . adjustment wall,5 . . . neutralizer, 5 a . . . adjustment wall, 4 . . . rotary drum, 4a, 4 a′ . . . substrate holder, 40 . . . motor, 50 . . . crystalmonitor, 51 . . . film thickness detector, 52 . . . controller, 53 . . .electric heater, 54 . . . temperature sensor, 60A . . . plasma treatmentregion, 60 . . . plasma generation means, 70 . . . reactive gas supplymeans, 71 . . . oxygen gas cylinder, 72 . . . massflow controller, 80A .. . sputtering region, 80 . . . sputtering means, 81 a, 81 b . . .sputtering electrode, 82 a, 82 b . . . target, 83 . . . transformer, 84. . . AC power supply, 90 . . . sputtering gas feeding means, 92 . . .sputtering gas cylinder.

MODES FOR CARRYING OUT THE INVENTION

Hereafter, embodiments of the aforementioned invention will be explainedwith reference to the drawings.

First Embodiment

In this embodiment, an example of the oil-repellent substrate isexplained.

As shown in FIG. 1, the oil-repellent substrate 100 of this embodimentcomprises the substrate 101, and the first film 103 is coated on atleast one surface of the substrate 101. On the first film 103, thesecond film 105 having oil repellency (henceforth referred to as“oil-repellent film”) is coated.

As the substrate 101, a plastic substrate (organic glass substrate) oran inorganic substrate (inorganic glass substrate) as well as asubstrate of metal such as stainless steel can be used, and thethickness thereof is, for example, 0.1 to 5 mm. Examples of theinorganic glass substrate, which is an example of the substrate 101,include, for example, those of soda lime glass (6H to 7H), borosilicateglass (6H to 7H), and so forth.

First, the first film 103 is deposited by using a dry depositionprocess. For example, when the first film 103 is constituted with SiO₂,if it is coated by a wet deposition process such as the sol-gel method,sufficient scratch resistance may not be imparted, and as a result, theoil-repellent film 105 having practically sufficient abrasionresistance, which is described later, may not be deposited. The firstfilm 103 is preferably constituted with a material showing pencilhardness higher than 9H measured by, for example, the method defined inJIS-K5600-5-4, including, for example, SiO₂, ZrO₂, Si₃N₄, Al₂O₃, and soforth. By coating the first film 103 consisting of a material havinghardness higher than the hardness of the substrate 101 on the surface ofthe substrate 101, it is made easier to improve the abrasion resistanceof the oil-repellent film 105 described later to a practicallysufficient level.

Second, the surface characteristics (surface roughness) of the firstfilm 103 are appropriately controlled so that appropriate concaves areformed on the surface. Specifically, center line average height (Ra),10-point average height (Rz), and maximum valley depth (Pv) areappropriately adjusted. All of Ra, Rz, and Pv are indices indicatingunevenness of the surface of the first film 103. In this embodiment,although the definition of the surface roughness (Ra, Rz, Pv) of thefirst film 103 is based on JIS-B0601, it is also surface roughness in aminute region or in a minute scale measured by using, for example, anon-contact surface roughness profiler, an atomic force microscope(AFM), or the like.

In order to improve abrasion resistance of the oil-repellent film 105described later to a practically sufficient level, the inventors of thepresent invention conducted researches for forming appropriate concaveson the surface of the first film 103 with paying attention to thespecific indices concerning the surface characteristics. As a result,they found that, by appropriately controlling values of Ra, Rz and Pvconcerning surface roughness among many parameters representing surfacecharacteristics, appropriate concaves were formed on the surface of thefirst film 103, and abrasion resistance of the oil-repellent film 105formed thereafter could be improved to a practically sufficient level.That is, since the surface characteristics of the first film 103according to this embodiment are appropriately controlled, abrasionresistance of the oil-repellent film 105 described later can be improvedto a practically sufficient level.

All of the center line average height (Ra), 10-point average height(Rz), and maximum valley depth (Pv) are indices representing unevennessof the surface of the first film 103.

According to this embodiment, Ra of the first film 103 is preferablyadjusted to be 0.1 nm or larger, more preferably 1 nm or larger, stillmore preferably 3 nm or larger. If Ra of the first film 103 is adjustedto be the predetermined value or larger, even after the surface of theoil-repellent film 105 described later is scratched by rubbing withsteel wool, components constituting the oil-repellent film 105(oil-repellent molecules) adhering to the concaves of the first film 103can be remained. As a result, expression of the oil repellency can besecured. On the other hand, when Ra of the first film 103 is too large,the oil repellency of the oil-repellent film 105 tends to be degraded.Therefore, in this embodiment, it is desirable that Ra of the first film103 is preferably adjusted to be 1000 nm or smaller, more preferably 100nm or smaller, still more preferably 20 nm or smaller.

According to this embodiment, Rz of the first film 103 is preferablyadjusted to be 5 nm or larger, more preferably 7 nm or larger, stillmore preferably 10 nm or larger. If Rz of the first film 103 is adjustedto be the predetermined value or larger, even after the surface of theoil-repellent film 105 described later is scratched by rubbing withsteel wool, components constituting the oil-repellent film 105(oil-repellent molecules) adhering to the concaves of the first film 103can be remained. As a result, expression of the oil repellency can besecured. On the other hand, when Rz of the first film 103 is too large,the oil repellency of the oil-repellent film 105 tends to be degraded.Therefore, in this embodiment, it is desirable that Rz of the first film103 is preferably adjusted to be 2000 nm or smaller, more preferably 200nm or smaller, still more preferably 50 nm or smaller.

According to this embodiment, Pv of the first film 103 is preferablyadjusted to be 15 nm or larger, more preferably 20 nm or larger, stillmore preferably 30 nm or larger. If Pv of the first film 103 is adjustedto be the predetermined value or larger, even after the surface of theoil-repellent film 105 described later is scratched by rubbing withsteel wool, components constituting the oil-repellent film 105(oil-repellent molecules) adhering to the concaves of the first film 103can be remained. As a result, expression of the oil repellency can besecured. On the other hand, when Pv of the first film 103 is too large,the oil repellency of the oil-repellent film 105 tends to be degraded.Therefore, in this embodiment, it is desirable that Pv of the first film103 is preferably adjusted to be 2000 nm or smaller, more preferably 300nm or smaller, still more preferably 150 nm or smaller.

The values of Ra, Rz and Pv are values measured according to JIS-B0601.

In this embodiment, the first film 103 is preferably prepared so thatappropriate concaves are formed on the surface thereof, and the convexesobserved on the surface thereof exist with predetermined periodicintervals. Specifically, it is desirable that convexes observed when thesurface roughness of the first film 103 is measured by linear scanningpreferably exist with periodic intervals of 0.1 to 5000 nm, morepreferably 1 to 1000 nm, still more preferably 1 to 50 nm.

The periodic interval of the convexes existing on the surface of thefirst film 103 referred to here means an interval λ between a certainconvex to the next convex beyond a concave between them in the surfaceprofile of the first film 103, and it can be calculated by dividing thelinearly scanned (measured) length with the number of peaks counted. Ifthe intervals of the convexes are adjusted to be within theaforementioned range, even after the surface of the oil-repellent film105 described later is scratched by rubbing with steel wool, componentsconstituting the oil-repellent film 105 (oil-repellent molecules)adhering to the concaves of the first film 103 can be remained. As aresult, expression of the oil repellency can be secured.

Such measurement of the periodic intervals of the convexes existing onthe surface of the first film 103 can be performed by using anon-contact surface profiler, an atomic force microscope (AFM), or thelike, as in the case of Ra, Rz, etc. mentioned above.

For the reasons described above, the first film 103 according to thisembodiment can be coated by a dry deposition process, for example, a dryplating method (PVD method) such as vacuum vapor deposition method(including ion-assisted deposition method), sputtering method,ion-plating method, and arcing deposition, not wet deposition process,with appropriately controlling the deposition conditions.

The first film 103 to be coated on the substrate 101 by the vacuum vapordeposition method, the sputtering method, or the like may be coated witha single layer or multiple layers. Thickness of the first film 103 atthis stage is, for example, about 3 to 1000 nm. If the thickness of thefirst film 103 at this stage is too small, there arises a problem thatthe first film 103 is totally shaved off thereafter by the irradiationof energy particles described later, and no longer remained. On theother hand, if the thickness of the first film 103 is too large, unevensurface roughness may not be appropriately imparted to the surface ofthe first film 103, even after irradiation of the energy particlesdescribed later.

According to this embodiment, after the first film 103 is deposited onthe substrate 101, this first film 103 is subjected to a treatment ofirradiating particles having energy (first irradiation treatment,postoperative irradiation). The particles having energy are irradiatedon the first film 103 in advance of the coating of the oil-repellentfilm 105 described later, in order to adjust the surface characteristicsof the first film 103 to be within the ranges described above.

Examples of the particles having energy include, for example, ion beamemitted by an ion gun, active species of reactive gas in plasma, and soforth. Therefore, when the first film 103 is coated by the ion-assisteddeposition method with an ion beam, for example, after completion of thedeposition, the irradiation conditions can be changed to predeterminedconditions, and then irradiation of the ion beam can be continued. Onthe other hand, when the first film 103 is deposited by repetition of asputtering step and a reaction step, after completion of this treatment,an ion beam can be irradiated with predetermined irradiation conditions.Alternatively, after the first film 103 is coated by repetition of asputtering step and a reaction step, active species in plasma for whichoperation conditions are changed to predetermined operation conditionsmay be irradiated on the first film 103.

Thickness of the first film 103 subjected to the postoperativeirradiation is, for example, 0.1 to 500 nm, preferably 5 to 50 nm.Unduly small or large thickness of the first film 103 at this stage mayresult in insufficient abrasion resistance of the surface, after thecoating of the oil-repellent film 105 described later.

The oil-repellent film 105 has a function of preventing adhesion of oilstains. The expression “preventing adhesion of oil stains” used heremeans to attain not only a condition that oil stains do not adhere, butalso a condition that oil stains can be easily wiped off, even if theyadhere.

That is, the oil-repellent film 105 maintains oil repellency.Specifically, abrasion resistance of the oil-repellent film 105 of thisembodiment is improved to such a practically sufficient level that evenafter it is reciprocally rubbed with steel wool #0000 at a load of 1kg/cm² over 500 times (preferably 1000 times), ink of oily pen adheringto it can be wiped off. The abrasion resistance is improved as describedabove, because appropriate concaves are formed on the surface of thebase for coating the oil-repellent film 105 (first film 103) by thetreatment of irradiating energy particles mentioned above, so that thesurface characteristics are controlled.

The oil-repellent film 105 can be constituted with an organic compoundhaving at least one hydrophobic group and at least one reactive groupthat can bind with hydroxyl group in the molecule (also referred tosimply as “hydrophobic reactive organic compound”), or the like.Examples of the hydrophobic reactive organic compound include, forexample, fluorine-containing organic compounds containing apolyfluoroether group or a polyfluoroalkyl group, and so forth.

Thickness of the oil-repellent film 105 is preferably 0.5 to 100 nm,more preferably 1 to 20 nm.

The oil-repellent film 105 can be deposited by, for example, using thevacuum vapor deposition method, chemical vapor deposition (CVD) method,or the like, with appropriately controlling the deposition conditionsthereof.

Although coating of the oil-repellent film 105 may be performedseparately from coating of the first film 103 with differentapparatuses, they are preferably performed successively in the sameapparatus. Such film deposition scheme can be attained by changing thedeposition source from the material for coating the first film 103 tothe material for coating the oil-repellent film 105. The coating of thefilms can also be performed with a single deposition apparatus byproviding a plurality of deposition sources.

In the oil-repellent substrate 100 according to this embodiment, thesurface characteristics of the first film 103 coated on at least onesurface of the substrate 101 are appropriately controlled as describedabove. Therefore, abrasion resistance of the oil-repellent film 105coated on the surface of the first film 103 is improved to a practicallysufficient level.

Therefore, the oil-repellent substrate 100 of this embodiment ispreferably applied to uses requiring oil repellency, for example,various displays (for example, plasma display panel (PDP), cathode raytube (CRT), liquid crystal display (LCD), electroluminescence display(ELD) etc.); showcases; cover glass such as that of watches and gauges;touch surfaces of touch-sensitive electronic equipments such as bankATMs and ticket machines; various electronic equipments having suchvarious displays as mentioned above such as cellular phones and personalcomputers; and so forth.

Second Embodiment

In this embodiment, an example of a film deposition system that enablesproduction of the oil-repellent substrate 100 of FIG. 1 is explained.

As shown in FIG. 2, the film deposition system 1 of this embodimentcomprises a vertically disposed cylindrical vacuum vessel 2. The vacuumvessel 2 is constituted so that it is evacuated by an evacuating means(not shown in the drawing) to a predetermined pressure. A load lockchamber may be connected to the vacuum vessel 2 via a door. If a loadlock chamber is provided, it becomes possible to carry in and out thesubstrate 101 with maintaining the vacuum in the vacuum vessel 2.

At an upper position in the vacuum vessel 2, a substrate holder 4 a′made of stainless steel having a spherical shape is rotatably heldaround a vertical axis. An aperture is provided at the center of thesubstrate holder 4 a′, and a crystal monitor 50 is disposed there. Thecrystal monitor 50 detects physical film thickness by a thicknessdetector 51 on the basis of change of the resonance frequency due todeposition of a thin film on the surface thereof. The result of filmthickness detection is sent to a controller 52.

In the inside of the vacuum vessel 2, an electric heater 53 is disposedso as to wrap the substrate holder 4 a′. Temperature of the substrateholder 4 a′ is detected with a temperature sensor 54 such as athermocouple, and the result is sent to the controller 52. Thecontroller 52 controls the electric heater 53 using output from thetemperature sensor 54 to appropriately control the temperature of thesubstrate 101.

At lower positions in the inside of the vacuum vessel 2, evaporationsources 34 and 36 for adhering materials for film deposition to thesubstrates 101 held by the substrate holder 4 a′, and an ion gun 38 forirradiating positive ions on the substrates 101 are disposed.

The evaporation source 34 is provided with a crucible (boat) 34 b havinga pitting for carrying a film deposition material on the upper part, anelectron gun 34 c for irradiating an electron beam (e⁻) on the filmdeposition material to evaporate it, and a shutter 34 a openably andclosably disposed at a position for intercepting the film depositionmaterial going to the substrates 101 from the crucible 34 b. When thefilm deposition material is put on the crucible 34 b, and electric poweris supplied to the electron gun 34 c by the electron gun power supply 34d to generate an electron beam from the electron gun 34 c and irradiatethis electron beam on the film deposition material, the film depositionmaterial is heated and evaporated. If the shutter 34 a is opened in sucha state, the film deposition material evaporating from the crucible 34 bmoves towards the substrates 101 in the inside of the vacuum vessel 2,and adheres to the surfaces of the substrates 101.

The evaporation source 36 is an evaporation source of resistance heatingtype such as those of direct heating type and indirect heating type inthis embodiment, and is provided with a crucible (boat) 36 b having apitting for carrying a film deposition material on the upper part, and ashutter 36 a openably and closably disposed at a position forintercepting the film deposition material going to the substrates 101from the crucible 36 b. According to the direct heating method,electrodes are attached to the metal boat to flow electric current so asto directly heat the metal boat using the boat itself as an electricalresistance heater, and heat the film deposition material put into it.The indirect heating method is a method in which the boat is not adirect heat source, and it is heated by applying an electric current toa heating means separately disposed apart from the boat, for example, adeposition filament consisting of a rare metal such as a transitionmetal. If the film deposition material put on the crucible 36 b isheated by the boat itself or a heater provided apart from the boat, andthe shutter 36 a is opened in this state, the film deposition materialevaporating from the crucible 36 b moves towards the substrates 101 inthe inside of the vacuum vessel 2, and adhere to the surfaces of thesubstrates 101.

The ion gun 38 is an ion source for ion assistance, and it withdrawscharged ions (O²⁺, Ar⁺) from plasma of reactive gas (O₂ etc.) or raregas (Ar etc.) and radiates them towards the substrates 101 withacceleration at a predetermined accelerating voltage. Above the ion gun38, a shutter 38 a is openably and closably disposed. Adjustment walls38 b and 38 b for adjusting directivity of the ions withdrawn by the iongun 38 are provided above the shutter 38 a.

With the collision energy of the cations irradiated from the ion gun 38,the film deposition material moved towards the substrates 101 from theevaporation sources 34 and 36 highly densely and firmly adheres to thesurfaces of the substrates 101. At this time, the substrate 101 ispositively charged with the cations contained in the ion beam.

In addition, there occurs a phenomenon that the whole substrate 101 ispositively charged (charge up) due to accumulation of cations radiatedfrom the ion gun 38 (for example, O²⁺) in the substrate 101. If chargeup occurs, abnormal discharge may occur between the positively chargedsubstrate 101 and another member, and the thin film (insulating layer)coated on the surface of the substrate 101 may be destroyed by impact ofthe discharge. Further, since the collision energy of the cationsradiated from the ion gun 38 is reduced by the positive charging of thesubstrate 101, denseness, adhesion strength, etc. of the thin film maybe decreased.

Therefore, according to this embodiment, in order to electricallyneutralize the positive charge accumulated in the substrate 101, aneutralizer 5 is disposed in the middle of the sidewall of the vacuumvessel 2. During the irradiation of the ion beam by the ion gun 38, theneutralizer 5 discharges electrons (e⁻) towards the substrate 101, thatis, it withdraws electrons from plasma of a rare gas such as Ar, andradiates them with acceleration by accelerating voltage. The electronsradiated from it neutralize electrification due to the ions adhering tothe surface of the substrate 101. In addition, adjustment walls 5 a and5 a for adjusting directivity of the electrons discharged from theneutralizer 5 are disposed above the neutralizer 5.

Hereafter, an example of the method for depositing a film using the filmdeposition system 1 will be explained.

In this embodiment, a case where metallic silicon (Si) or silicon oxide(SiO₂) is used as the first film deposition material charged in the boatof the evaporation source 34 is exemplified. The second film depositionmaterial as a material for coating the oil-repellent film charged in theboat of the evaporation source 36 is not particularly limited.

Further, in this embodiment, there is exemplified a case where the firstfilm 103 is deposited by the ion-beam assisted deposition method (IAD)using an ion gun, the first irradiation treatment (postoperativeirradiation) is carried out with an ion beam generated by the ion gunfor the first film 103, and the oil-repellent film 105 is deposited bythe vacuum vapor deposition method of resistance heating type.

Form of the first film deposition material is not particularly limited,and for example, the material in the form of a pellet can be used. Theheating method for the first film deposition material is not limited tothe electron beam heating method, and a heat source enabling sufficientheating for evaporating the deposition material, such as halogen lamp,sheathed heater, resistance heating, and induction heating can be used.

Form of the second film deposition material is not particularly limited,and for example, (a) a hydrophobic reactive organic compound impregnatedin porous ceramics, or (b) a hydrophobic reactive organic compoundimpregnated in a mass of metal fibers or filaments can be used. Thesecan quickly absorb a lot of the hydrophobic reactive organic compound,and evaporate it. The porous ceramics is preferably used in the form ofpellet in view of handling property.

Examples of the metal fibers or filaments include, for example, those ofiron, platinum, silver, copper, and so forth. As the metal fibers orfilaments, it is preferable to use those of such an entangled state thatthey can hold a sufficient amount of the hydrophobic reactive organiccompound, for example, those in the form of woven fabric or nonwovenfabric. Void ratio of the mass of metal fibers or filaments can bedetermined according to amount of the hydrophobic reactive organiccompound to be held.

When a mass of metal fibers or filaments is used for the second filmdeposition material, it is preferably held in a container of which oneend is opened. The mass of metal fibers or filaments held in a containercan also be regarded as a pellet. Although shape of the container is notparticularly limited, examples include those of Knudsen type, divergentnozzle type, straight cylinder type, divergent cylinder type, boat type,filament type, and so forth, and type of the container can be suitablychosen according to the specification of the vapor deposition apparatus.At least one end of the container is opened, so that the hydrophobicreactive organic compound evaporates from the open end. As the materialof the container, metals such as copper, tungsten, tantalum, molybdenumand nickel, ceramics such as alumina, carbon, and so forth can be used,and it is appropriately chosen according to types of the vapordeposition apparatus, the hydrophobic reactive organic compound, and soforth.

Sizes of both the porous ceramic pellet and the pellet consisting of amass of metal fibers or filaments held in a container are not limited.

When porous ceramics or a mass of metal fibers or filaments isimpregnated with the hydrophobic reactive organic compound, a solutionof the hydrophobic reactive organic compound in an organic solvent isprepared first, porous ceramics or a mass of metal fibers or filamentsis impregnated with the solution by the dipping method, dropping method,spraying method, or the like, and then the organic solvent isevaporated. Since the hydrophobic reactive organic compound has areactive group (hydrolysable group), it is preferable to use an inertorganic solvent.

Examples of the inert organic solvent include fluorine-modifiedaliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane,etc.), fluorine-modified aromatic hydrocarbon solvents (m-xylenehexafluoride, benzotrifluoride etc.), fluorine-modified ether solvents(methyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran) etc.),fluorine-modified alkylamine solvents (perfluorotributylamine,perfluorotripentylamine etc.), hydrocarbon solvents (toluene, xyleneetc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutylketone etc.), and so forth. These organic solvents can be usedindependently or as any combination of two or more kinds of them.Concentration of the hydrophobic reactive organic compound solution isnot limited, and it can be appropriately determined according to shapeof the carrier to be impregnated with the hydrophobic reactive organiccompound.

The method for heating the second film deposition material is notlimited to the resistance heating method, and a halogen lamp, sheathedheater, electron beam, plasma electron beam, induction heating, and soforth can be used.

(1) First, a plurality of the substrates 101 are fixed on the substrateholder 4 a′. The substrates 101 fixed on the substrate holder 4 a′ canbe constituted from glass, plastics or metal processed into a tabularshape, lenticular shape, or the like. In addition, the substrates 101are preferably subjected to wet cleaning before or after the fixation.(2) Then, after the substrate holder 4 a′ is set in the inside of thevacuum vessel 2, the inside of the vacuum vessel 2 is evacuated to about10⁻⁴ to 10⁻² Pa. If the pressure is lower than 10⁻⁴ Pa, too much timemay be required for the evacuation to degrade the productivity. On theother hand, if the pressure is higher than 10⁻² Pa, film deposition maybecome insufficient, and thus film characteristics may be degraded.(3) Then, the electric heater 53 is electrified and thereby made togenerate heat, and the substrate holder 4 a′ is rotated at a low speed.This rotation provides uniform temperature and uniform film depositionconditions of a plurality of the substrates 101.

When the controller 52 determines that the temperature of the substrates101 has reached a temperature of from ordinary temperature to 120° C.,preferably 50 to 90° C., according to the output of the temperaturesensor 54, it starts the film deposition step. If the substratetemperature is lower than ordinary temperature, there is observed atendency that density of the first film 103 to be deposited becomes low,and sufficient durability of the film cannot be obtained. If thesubstrate temperature exceeds 120° C., plastic substrates used as thesubstrates 101 may be degraded or deformed. In addition, when a materialsuitable for unheated film deposition is used, the film deposition maybe carried out at ordinary temperature.

In this embodiment, before starting the film deposition step, the iongun 38 is made to be in an idling operation state. Further, theevaporation sources 34 and 36 are also prepared so that the first filmdeposition material and the second film deposition material can beimmediately diffused (discharged) by opening operation of the shutters34 a and 36 a.

(4) Then, the controller 52 increases the irradiation electric power forthe ion gun 38 from that of the idling state to a predeterminedirradiation power, and opens the shutter 38 a and the shutter 34 a toperform ion beam-assisted deposition (IAD) of the first film depositionmaterial. The operation of the neutralizer 5 is also started at thistime. That is, the step of dispersing the first film deposition materialfrom the evaporation source 34, the step of irradiating an ion beam ofintroduced gas (oxygen in this case) withdrawn from the ion gun 38, andthe step of irradiating electrons, to the film deposition surface of thesubstrate 101, are performed in parallel (first film depositionprocess).

The assisting conditions of the ion beam are as follows. As for type ofthe gas introduced into the ion gun 38, for example, oxygen, argon, or amixed gas of oxygen and argon is preferred. Volume of the gas of theaforementioned type introduced into the ion gun 38 is, for example, 1 to100 sccm, preferably 5 to 50 sccm. The unit “sccm” is an abbreviationfor “standard cc/m”, and indicates a value at 0° C. and 101.3 kPa (1atmosphere).

The accelerating voltage (V1) of the ions is, for example, 100 to 2000V, preferably 200 to 1500 V. The current density (I1) of the ions is,for example, 1 to 120 μA/cm², preferably 5 to 50 μA/cm².

The irradiation time (T1) of the ions is, for example, 1 to 800 seconds,preferably 10 to 100 seconds. The value obtained by dividing the productof I1 and T1 with the elementary electric charge of electron e(=1.602×10⁻¹⁹ C) (=(I1×T1)/e) represents number of ions to beirradiated, and in this embodiment, the ion beam can be irradiated at anirradiated ion number in the range of, for example, 1×10¹³ to 5×10¹⁷ions/cm², preferably 5×10¹³ to 5×10¹⁴ ions/cm².

In addition, the irradiation energy density (=V1×I1×T1) can also becontrolled by, for example, shortening the irradiation time (T1) forincreasing the irradiation electric power density, or lengthening theirradiation time (T1) for decreasing the irradiation electric powerdensity.

The operation conditions of the neutralizer 5 are as follows. As fortype of the gas introduced into the neutralizer 5, it is, for example,argon. Introduction volume of the gas of the aforementioned type is, forexample, 10 to 100 sccm, preferably 30 to 50 sccm. The acceleratingvoltage of electrons is, for example, 20 to 80 V, preferably 30 to 70 V.The electronic current may be such a current that an electric currenthigher than the ionic current is supplied.

As the first film 103, three-dimensional nuclei are deposited on thesubstrate 101 first at an early stage of the film deposition, and thenthey grow with increase of the film deposition amount (vapor depositionamount), combine together, and eventually grow into a continuous film(island growth).

As described above, the first film 103 consisting of SiO₂ is depositedon the surface of the substrate 101 with a predetermined thickness. Thecontroller 52 continues monitoring of the thickness of the thin filmcoated on the substrate 101 with the crystal monitor 50, and when itreaches a predetermined thickness, the controller 52 terminates the filmdeposition.

(5) Then, when the controller 52 terminates the film deposition, itcloses only the shutter 34 a, while the shutter 38 a is maintained to beopened. In this state, the controller 52 changes the irradiationelectric power of the ion gun 38 to a predetermined irradiation electricpower, and continues the irradiation of ion beam. This step is anexample of the first irradiation treatment (postoperative irradiation).This embodiment is characterized in that a postoperative irradiation isperformed for the first film 103 coated on the surface of the substrate101.

By performing the postoperative irradiation, a surface portion of thefirst film 103 is shaved off, and as a result, appropriate concaves areprovided on the surface of the first film 103.

Conditions of the postoperative irradiation are as follows. As for typeof the gas introduced into the ion gun 38, it is sufficient that itcontains at least argon or oxygen, and it may be a mixed gas of argonand oxygen, but it preferably contains at least argon. Volume to beintroduced of the gas of the aforementioned type (total volume in thecase of a mixed gas) is, for example, 10 to 100 sccm, preferably 20 to70 sccm.

The accelerating voltage (V2) of the ions is, for example, 100 to 2000V, preferably 200 to 1500 V. The current density (12) of the ions is,for example, 1 to 120 μA/cm², preferably 5 to 50 μA/cm².

The irradiation time (T2) of the ions is, for example, 1 to 800 seconds,preferably 10 to 100 seconds. The value obtained by dividing the productof I2 and T2 with the elementary electric charge of electron e(=1.602×10⁻¹⁹ C) (=(I2×T2)/e) represents number of ions to beirradiated, and the ion beam can be irradiated at an irradiated ionnumber in the range of, for example, 1×10¹³ to 5×10¹⁷ ions/cm²,preferably 1×10¹³ to 1×10¹⁷ ions/cm², more preferably 1×10¹⁴ to 1×10¹⁶ions/cm².

In addition, the irradiation energy density (=V2×I2×T2) can also becontrolled by, for example, shortening the irradiation time (T2) forincreasing the irradiation electric power density, or lengthening theirradiation time (T2) for decreasing the irradiation electric powerdensity.

(6) Then, the controller 52 returns the irradiation electric power ofthe ion gun 38 to the level of the idling state, closes the shutter 38a, and opens the shutter 36 a to perform vacuum vapor deposition of thesecond film deposition material as a raw material for coating anoil-repellent film by the resistance heating method. That is, to thesurface of the first film 103 subjected to the postoperativeirradiation, the second film deposition material is dispersed, forexample, for 3 to 20 minutes, from the evaporation source 36 to performthe film deposition process (second film deposition process).

As a result, the oil-repellent film 105 is coated on the first film 103subjected to the postoperative irradiation in a predetermined thickness(for example, 1 to 50 nm). The controller 52 continues monitoring of thethickness of the thin film deposited on the first film 103 with thecrystal monitor 50, and when it reaches a predetermined thickness, thecontroller 52 terminates the vapor deposition. By the aforementionedsteps, the oil-repellent substrate 100 shown in FIG. 1 is produced.

According to the method for depositing a film using the film depositionsystem 1 of this embodiment, an ion beam of the gas to be introduced asan example of the energy particles is irradiated on the first film 103coated on the surface of the substrate 101 in advance of the filmdeposition of the oil-repellent film 105 (postoperative irradiation).Appropriate concaves are thereby provided on the surface of the firstfilm 103 subjected to the ion beam irradiation. Accordingly, theoil-repellent molecules as constituent components of the oil-repellentfilm 105 to be deposited thereafter can be adhered also to the concavesof the first film 103. By adhering the constituent components of theoil-repellent film 105 to the concaves of the first film 103, even ifoil components such as fingerprint components adhering to the surface ofthe oil-repellent film 105 are wiped off with a heavy load (for example,load of about 1 kg/cm²), the constituent components of the oil-repellentfilm 105 can be effectively remained on the outermost surface. That is,according to this embodiment, it becomes possible to coat theoil-repellent film 105 having abrasion resistance of a practicallysufficient level.

For this embodiment, an example where only the SiO₂ thin film is coatedas the first film 103 on the substrate 101 is described. However,together with this SiO₂ thin film, another thin film such as a Si₃N₄thin film and a ZrO₂ thin film can also be deposited. Further, as thefirst film 103 coated on the substrate 101, another thin film such as aSi₃N₄ thin film and a ZrO₂ thin film may be coated instead of the SiO₂thin film. For this purpose, the material or shape of the first filmdeposition material charged in the deposition source 34 may be changedin any of these cases.

Further, in this embodiment, a surface treatment of the substrate 101can also be performed in advance of the first film deposition process.Specific examples of such a surface treatment include 1) plasmatreatment under an oxygen or argon atmosphere, 2) chemical treatmentwith an acid or an alkali, 3) irradiation treatment with particleshaving energy by the ion gun 38 (second irradiation treatment,preoperative irradiation), and so forth. Among these, the secondirradiation treatment (preoperative irradiation) is preferred. If thesecond irradiation treatment (preoperative irradiation) is performed forthe substrate 101 in advance of the first film deposition process, thecontroller 52 can increase the irradiation electric power for the iongun 38 from the level of the idling state to a predetermined level ofirradiation electric power, open the shutter 38 a and irradiate an ionbeam on the surface of the substrate 101 in the middle of the rotationbefore the first film deposition process. By performing the preoperativeirradiation for the substrate 101 before performing the postoperativeirradiation for the first film 103 deposited on the substrate 101, moreappropriate concaves can be provided on the surface of the first film103.

The conditions of the preoperative irradiation may be the same as ordifferent from those of the postoperative irradiation mentioned above.

For example, the conditions of the preoperative irradiation are asfollows. As for type of the gas introduced into the ion gun 38, it issufficient that it contains at least argon or oxygen, and it may be amixed gas of argon and oxygen. However, it is preferably a mixed gas ofargon and oxygen. Volume to be introduced of the gas of theaforementioned type (total volume in the case of a mixed gas) is, forexample, 10 to 100 sccm, preferably 20 to 70 sccm.

The accelerating voltage (V3) of the ions is, for example, 100 to 2000V, preferably 200 to 1500 V. The current density (I3) of the ions is,for example, 1 to 120 μA/cm², preferably 5 to 50 μA/cm².

The irradiation time (T3) of the ions is, for example, 60 to 1200seconds, preferably 120 to 900 seconds, more preferably 180 to 720seconds. The value obtained by dividing the product of I3 and T3 withthe elementary electric charge of electron e (=1.602×10⁻¹⁹ C)(=(I3×T3)/e) represents number of ions to be irradiated, and in thisembodiment, the ion beam is preferably irradiated at an irradiated ionnumber in the range of, for example, 5×10¹⁴ to 5×10¹⁷ ions/cm²,preferably 1×10¹⁵ to 1×10¹⁷ ions/cm², more preferably 1×10¹⁶ to 1×10¹⁷ions/cm².

In addition, the irradiation energy density (=V3×I3×T3) can also becontrolled by, for example, shortening the irradiation time (T3) forincreasing the irradiation electric power density, or lengthening theirradiation time (T3) for decreasing the irradiation electric powerdensity.

Further, depending on the conditions of the ion-assisted deposition withthe ion beam in the step (4) mentioned above, the surface of the firstfilm 103 may have unevenness before the postoperative irradiation of thestep (5) mentioned above is performed. In such a case, the concavesalready exist on the first film 103 may be shaved off first by thepostoperative irradiation of the step (5) mentioned above, and thesubstrate 101 may be exposed. This embodiment also includes anembodiment in which a part of the substrate 101 is exposed by thepostoperative irradiation.

Third Embodiment

In this embodiment, another example of the film deposition systemenabling production of the oil-repellent substrate 100 of FIG. 1 isexplained. The same numerical notations as those of the secondembodiment are given to the same members, and explanations thereof areomitted.

As shown in FIG. 3, the film deposition system 1 a of this embodimentcomprises a vacuum vessel 2. At an upper position in the inside of thevacuum vessel 2, a rotary drum 4 is rotatably held around an axisperpendicular to the vertical axis. The rotary drum 4 as a substrateholding mechanism is a cylindrical member for holding the substrate 101on which film deposition is performed in the inside of the vacuum vessel2.

As shown in FIG. 4, the rotary drum 4 comprises a plurality of substrateholders 4 a, frames 4 b, and connection means 4 c for connecting thesubstrate holders 4 a and the frames 4 b.

The substrate holder 4 a has a plurality of substrate holding holes forholding the substrates 101 on a center part of the plate surface in arow along the longer direction of the substrate holder 4 a. Thesubstrate 101 is held in the substrate holding hole of the substrateholder 4 a, and fixed to the substrate holder 4 a with a screw member orthe like so that it should not drop out of the holder. Further, at theboth ends of the substrate holder 4 a along the longer direction(z-direction), screw holes into which the connection means 4 c can beinserted are provided on the plate surface.

The frame 4 b consists of two ring members disposed on the upper andlower sides (x-direction). In each of the ring members, screw holes areprovided at positions corresponding to the screw holes of the substrateholder 4 a. The substrate holder 4 a and the frame 4 b are fixed byusing the connection means 4 c consisting of, for example, a bolt and anut.

The rotary drum 4 is constituted so that it can move between the insideof the vacuum vessel 2 and a load lock chamber connected to the vacuumvessel 2 through a door. The rotary drum 4 is disposed in the inside ofthe vacuum vessel 2 so that the central axis line Z1 along thecylindrical direction of the cylinder (z-direction) corresponds to theanterior-posterior direction of the vacuum vessel 2 (z-direction).

When the substrate holder 4 a is attached to the frame 4 b or detachedfrom the frame 4 b, the rotary drum 4 is conveyed to the load lockchamber, and the substrate holder 4 a is detached from and attached tothe frame 4 b in this load lock chamber. On the other hand, at the timeof film deposition, the rotary drum 4 is conveyed to the inside of thevacuum vessel 2, and rotatably disposed in the vacuum vessel 2.

The posterior surface center part of the rotary drum 4 has a shape thatcan engage with the front of a motor rotating shaft 40 a. The rotarydrum 4 and the motor rotating shaft 40 a are positioned so that thecentral axis line of the motor rotating shaft 40 a and the central axisline Z1 of the rotary drum 4 should coincide with each other, and areconnected by engagement of them. The surface of the rotary drum 4 in theposterior surface thereof that engages with the motor rotating shaft 40a consists of an insulating member. Abnormal discharge of the substrate101 can be thereby prevented. Further, airtightness between the vacuumvessel 2 and the motor rotating shaft 40 a is maintained with an O-ring.

The motor rotating shaft 40 a is rotated by driving a motor 40 providedbehind the vacuum vessel 2 in a state that vacuum in the inside of thevacuum vessel 2 is maintained. With this rotation, the rotary drum 4connected with the motor rotating shaft 40 a rotates around the axisline Z1. Since each substrate 101 is held on the rotary drum 4, itrevolves around the axis line Z1 as a revolution axis with rotation ofthe rotary drum 4.

The drum-rotating shaft 42 is provided on the front of the rotary drum4, and the drum-rotating shaft 42 also rotates with the rotation of therotary drum 4. A hole is formed in the front wall (z-direction) of thevacuum vessel 2, and the drum-rotating shaft 42 penetrates this hole andleads to the outside of the vacuum vessel 2. Bearing is provided on theinternal surface of the hole and allows smooth rotation of the rotarydrum 4. Between the vacuum vessel 2 and the drum-rotating shaft 42,airtightness is maintained with an O-ring.

<<Sputtering Region and Sputtering Means>>

Returning back to FIG. 3, a partition wall 12 is provided on the side ofthe vacuum vessel 2 in the vertical direction (x-direction) at aposition facing the rotary drum 4. The partition wall 12 is a membermade from the same stainless steel as that of the vacuum vessel 2. Thepartition wall 12 is constituted by planar members each disposed up anddown, and left and right, and disposed from the internal wall of thevacuum vessel 2 towards the rotary drum 4 so as to form a closed square.A sputtering region 80A is thereby partitioned in the inside of thevacuum vessel 2.

The sidewall of the vacuum vessel 2 has a section having a convexprojecting outward, and a sputtering means 80 is provided on theprojecting wall surface.

The sputtering region 80A is formed in a region surrounded by theinternal wall of the vacuum vessel 2, the partition wall 12, theexternal surface of the rotary drum 4, and the sputtering means 80. Inthe sputtering region 80A, a sputtering treatment for depositing a filmmaterial on the surface of the substrate 101 is performed.

As shown in FIG. 5, the sputtering means 80 is constituted by a pair oftargets 82 a and 82 b, a pair of sputtering electrodes 81 a and 81 bholding the targets 82 a and 82 b, an AC power supply 84 for supplyingelectric power to the sputtering electrodes 81 a and 81 b, and atransformer 83 as an electric power control means for controllingelectric power from the AC power supply 84.

The wall surface of the vacuum vessel 2 is projected outward, and thesputtering electrodes 81 a and 81 b are disposed on the internal wall ofthe vacuum vessel 2 at the projected portion so as to penetrate thesidewall. These sputtering electrodes 81 a and 81 b are fixed to thevacuum vessel 2 at the earth potential via insulating members.

The targets 82 a and 82 b consist of the first film deposition materialformed in the form of a plate, and they are held by the sputteringelectrodes 81 a and 81 b, respectively, so as to face the side of therotary drum 4 as described later. In this embodiment, as the targets 82a and 82 b, a material to which hardness higher than the hardness of thesubstrate 101 can be imparted by oxidation, nitridation oroxynitridation, such as metallic silicon (Si), aluminum (Al) andzirconium (Zr), is used. In this embodiment, use of a Si target isexemplified.

The sputtering electrodes 81 a and 81 b have a structure that aplurality of magnets are disposed in a predetermined direction. Thesputtering electrodes 81 a and 81 b are connected to the AC power supply84 via the transformer 83, and constituted so that an alternatingelectric field of 1 to 100 kHz can be applied to the both electrodes.The targets 82 a and 82 b are held by the sputtering electrodes 81 a and81 b, respectively. The targets 82 a and 82 b have a plate shape, and asshown in FIG. 2, the targets 82 a and 82 b are disposed so that thelonger direction thereof is parallel to the rotating-shaft line Z1 ofthe rotary drum 4.

A sputtering gas feeding means 90 for supplying a sputtering gas such asargon is provided around the sputtering region 80A. The sputtering gasfeeding means 90 comprises a sputtering gas cylinder 92 as a sputteringgas storage means, piping 95 a and piping 95 c as a sputtering gassupply route, and a massflow controller 91 as a sputtering gas flow ratecontrol means for controlling flow rate of the sputtering gas.

Examples of the sputtering gas include, for example, an inert gas suchas argon and helium.

The sputtering gas cylinder 92 and the massflow controller 91 are bothprovided outside the vacuum vessel 2. The massflow controller 91 isconnected to the single sputtering gas cylinder 92 storing thesputtering gas via the piping 95 c. The massflow controller 91 isconnected to the piping 95 a, and one end of the piping 95 a penetratesthe sidewall of the vacuum vessel 2 and leads to neighborhood of thetargets 82 a and 82 b in the sputtering region 80A.

The end of the piping 95 a is disposed below the targets 82 a and 82 bnear the center of them, and a feed port 95 b is opened at the tipthereof towards the center of the front surfaces of the targets 82 a and82 b.

The massflow controller 91 is an apparatus for controlling flow rate ofthe gas, and comprises an inlet through which the gas from thesputtering gas cylinder 92 flows in, an outlet for flowing thesputtering gas into the piping 95 a, a sensor for detecting massflowrate of the gas, a control valve for controlling flow rate of the gas, asensor for detecting massflow rate of the gas flown in via the inlet,and an electronic circuit for controlling the control valve on the basisof the flow rate detected by the sensor. The electronic circuit isdesigned so that a desired flow rate can be set from the outside.

The sputtering gas fed from the sputtering gas cylinder 92 is introducedinto the piping 95 a at a flow rate controlled by the massflowcontroller 91. The sputtering gas flown into the piping 95 a isintroduced from the feed port 95 b into the region in front of thetargets 82 a and 82 b disposed in the sputtering region 80A.

In a state that the sputtering gas is supplied to the sputtering region80A by the sputtering gas feeding means 90, and the targets 82 a and 82b are surrounded by an inert gas atmosphere, if an alternate current isapplied to the sputtering electrodes 81 a and 81 b from the AC powersupply 84, a part of the sputtering gas around the targets 82 a and 82 bemits electrons, and it is thereby ionized. Since a leakage magneticfield is formed on the surfaces of the targets 82 a and 82 b by themagnets disposed in the sputtering electrodes 81 a and 81 b, thoseelectrons go around in the magnetic field generated near the surfaces ofthe targets 82 a and 82 b with describing a toroidal curve. Intenseplasma is generated along the orbits of the electrons, and ions of thesputtering gas are accelerated towards the plasma, and collide with thetargets 82 a and 82 b to drive out atoms and particles of the surfacesof the targets 82 a and 82 b (Si atoms and Si particles when the targets82 a and 82 b consist of Si). The Si atoms and Si particles driven outadhere to the surface of the substrate 101 to coat a microfilm.

<<Plasma Treatment Region and Plasma Generation Means>>

Returning back to FIG. 3, a partition wall 14 is disposed on the upperinternal wall of the vacuum vessel 2 in the vertical direction(x-direction) at a position facing the rotary drum 4. The partition wall14 is a member made from, for example, the same stainless steel as thatof the vacuum vessel 2. The partition wall 14 is constituted by planarmembers each disposed up and down, and left and right, and disposed fromthe internal wall of the vacuum vessel 2 towards the rotary drum 4 so asto form a closed square. A plasma treatment region 60A is therebypartitioned in the inside of the vacuum vessel 2. Thus, in thisembodiment, the plasma treatment region 60A is provided at a positionopposite to the vapor deposition region 30A with respect to the rotarydrum 4 (upper part of the vacuum vessel 2 in the vertical direction, ina direction of substantially 180° from the vapor deposition region 30A),remote from the sputtering region 80A by an angle of substantially 90°,and spatially separated from both the vapor deposition region 30A andthe sputtering region 80A.

The upper internal wall of the vacuum vessel 2 has a section having aconvex projecting outward (upward), and a plasma generation means 60 isprovided on the projected wall surface so as to face the plasmatreatment region 60A.

The plasma treatment region 60A is formed in a region surrounded by theinternal wall surface of the vacuum vessel 2, the partition wall 14, theexternal surface of the rotary drum 4, and the plasma generation means60, and coats a thin film consisting of a compound orincompletely-reacted compound of Si by a reactive treatment of themicrofilm adhered to the surface of the substrate 101 in the sputteringregion 80A.

As shown in FIG. 6, at a position on the upper wall surface of thevacuum vessel 2 corresponding to the plasma treatment region 60A, a hole2 a for installing the plasma generation means 60 is formed. Further,the piping 75 a is connected to the plasma treatment region 60A. Themassflow controller 72 is connected to one end of the piping 75 a, andthis massflow controller 72 is further connected to the reactive gascylinder 71. Therefore, the reactive gas can be supplied from thereactive gas cylinder 71 into the plasma treatment region 60A.

The plasma generation means 60 comprises a case 61, a dielectric plate62, an antenna 63, a matching box 64, and a radio frequency power supply65.

The case 61 has a shape closing the hole 2 a formed on the wall surfaceof the vacuum vessel 2, and is fixed with bolts so as to close the hole2 a of the vacuum vessel 2. By fixing the case 61 on the wall surface ofthe vacuum vessel 2, the plasma generation means 60 is attached to thewall surface of the vacuum vessel 2. The case 61 is formed withstainless steel.

The dielectric plate 62 is formed with a tabular dielectric substance.Although the dielectric plate 62 is formed with quartz in thisembodiment, the material of the dielectric plate 62 is not limited toquartz, and it may be one formed with a ceramic material such as Al₂O₃.The dielectric plate 62 is fixed to the case 61 with a fixing frame. Byfixing the dielectric plate 62 to the case 61, an antenna housing 61A isformed in a region surrounded by the case 61 and the dielectric plate62.

The dielectric plate 62 fixed to the case 61 is disposed so as to facethe inside of the vacuum vessel 2 (plasma treatment region 60A) throughthe hole 2 a. In this configuration, the antenna housing 61A isseparated from the inside of the vacuum vessel 2. That is, the antennahousing 61A and the inside of the vacuum vessel 2 are partitioned by thedielectric plate 62 to form independent spaces. Further, the antennahousing 61A and the outside of the vacuum vessel 2 are partitioned bythe case 61 to form independent spaces. In this embodiment, the antenna63 is disposed in the antenna housing 61A formed as an independent spaceas described above. In addition, airtightness between the antennahousing 61A and the inside of the vacuum vessel 2, and between theantenna housing 61A and the outside of the vacuum vessel 2 is maintainedwith an O-ring, respectively.

In this embodiment, a piping 16 a-2 is branched from a piping 16 a-1.This piping 16 a-2 is connected to the antenna housing 61A, and has arole of functioning as an exhausting pipe at the time of evacuating theinside of the antenna housing 61A to obtain vacuum.

Valves V1 and V2 are provided in the piping 16 a-1 at positions on theway of from a vacuum pump 15 a to the inside of the vacuum vessel 2.Further, a valve V3 is provided in the piping 16 a-2 at a position onthe way of from the vacuum pump 15 a to the antenna housing 61A. Byclosing either one of the valves V2 and V3, movement of gas between theinsides of the antenna housing 61A and the vacuum vessel 2 is prevented.Internal pressure of the vacuum vessel 2 and internal pressure of theantenna housing 61A are measured with a vacuum gage.

The film deposition system 1 a of this embodiment (refer to FIG. 3) isprovided with a control unit. Output of the vacuum gage is inputted intothis control unit. The control unit has a function of controllingevacuation by the vacuum pump 15 a on the basis of the inputted valuemeasured by the vacuum gage to adjust degree of vacuum in the inside ofthe vacuum vessel 2 and the inside of the antenna housing 61A. Accordingto this embodiment, the control unit controls opening and closing of thevalves V1, V2, and V3, and thereby the insides of the vacuum vessel 2and the antenna housing 61A can be independently or simultaneouslyevacuated.

According to this embodiment, by appropriately controlling the vacuumpump 15 a, film deposition atmosphere in the sputtering region 80A canbe stabilized.

The antenna 63 is a means for being supplied electric power from theradio frequency power supply 65 to generate an induction field insidethe vacuum vessel 2 (plasma treatment region 60A) and generate plasma inthe plasma treatment region 60A. The antenna 63 comprises a tubular bodyformed with copper, and a covering layer covering the body surface andformed with silver. That is, the body of the antenna 63 is formed withinexpensive and easily processable copper, which also shows low electricresistance, in the form of tube, and the surface of the antenna 63 iscovered with silver of which electric resistance is lower than that ofcopper. The impedance of the antenna 63 for radio frequency is therebyreduced to efficiently flow an electric current through the antenna 63and improve the efficiency of generation of plasma.

The film deposition system 1 a of this embodiment (refer to FIG. 3) isconfigured so that an alternating voltage having a frequency of 1 to 27MHz is applied to the antenna 63 from the radio frequency power supply65 to generate plasma of a reactive gas in the plasma treatment region60A.

The antenna 63 is connected to the radio frequency power supply 65 viathe matching box 64 holding a matching circuit. In the matching box 64,a variable capacitor not shown in the drawing is provided.

The antenna 63 is connected to the matching box 64 via a lead wire. Thelead wire consists of a material similar to that of the antenna 63. Onthe case 61, an insertion hole for inserting the lead wire is formed,and the antenna 63 in the antenna housing 61A and the matching box 64outside the antenna housing 61A are connected via the lead wire insertedinto the insertion hole. A sealing member is provided between the leadwire and the insertion hole to maintain airtightness between the insideand outside of the antenna housing 61A.

Between the antenna 63 and the rotary drum 4, a grid 66 may be providedas an ion-annihilating means. The grid 66 is for annihilating a part ofions and a part of electrons generated by the antenna 63. The grid 66 isa hollow member consisting of an electric conductor, and is grounded. Inorder to flow a cooling medium (for example, cooling water) inside thegrid 66 consisting of a hollow member, a hose for supplying a coolingmedium is connected to the end of the grid 66.

Further, the reactive gas supply means 70 is disposed in the plasmatreatment region 60A and around it. The reactive gas supply means 70 ofthis embodiment comprises the reactive gas cylinder 71 for storing areactive gas (for example, oxygen gas, nitrogen gas, fluorine gas, ozonegas, etc.), the massflow controller 72 for controlling flow rate of thereactive gas supplied from the reactive gas cylinder 71, and the piping75 a for introducing the reactive gas into the plasma treatment region60A.

When the rotary drum 4 is rotated by the motor 40 (refer to FIG. 4), thesubstrate 101 held on the outer surface of the rotary drum 4 revolvesand repeatedly moves from a position facing the sputtering region 80A toa position facing the plasma treatment region 60A, or vice versa. As aresult of such revolution of the substrate 101 as described above, thesubstrate 101 is successively and repeatedly subjected to a sputteringtreatment in the sputtering region 80A and a plasma treatment in theplasma treatment region 60A, and a thin film (first film 103) is therebycoated on the surface of the substrate 101. In particular, when electricpower is supplied to the antenna 63 from the radio frequency powersupply 65 in a state that the reactive gas is introduced into the plasmatreatment region 60A from the reactive gas cylinder 71 via the piping 75a, plasma is generated in a region facing the antenna 63 in the plasmatreatment region 60A, and the first film deposition material depositedon the surface of the substrate 101 is densified to coat a thin film(first film 103) having sufficient characteristics.

<<Vapor Deposition Region, Vapor Deposition Source and Ion Gun>>

Returning back to FIG. 3, the vapor deposition region 30A is provided ata lower part of the vacuum vessel 2 in the vertical direction(x-direction). The vapor deposition region 30A is a region for coatingthe oil-repellent film 105 by vapor deposition on the surface of thefirst film 103 coated on the surface of the substrate 101.

Below the vapor deposition region 30A (on the internal bottom wall ofthe vacuum vessel 2), a vapor deposition source 36 of resistance heatingtype is provided. Since the configuration of the vapor deposition source36 is the same as that of the second embodiment, explanation thereof isomitted.

A piping 23 for evacuation is connected to the internal bottom wall ofthe vacuum vessel 2, and a vacuum pump 24 for evacuating a space aroundthe deposition source 36 is connected to the piping 23. The degree ofvacuum in the vacuum vessel 2 can be controlled by the vacuum pump 24and a controller (not shown in the drawing).

A door 3 is provided on the side of the vacuum vessel 2 (z-direction),and the door 3 is opened and closed by sliding or rotating it. A loadlock chamber may be separately connected outside the door 3.

According to this embodiment, the ion gun 38 is further disposed at alower part of the vacuum vessel 2 in the vertical direction(x-direction). Since the configuration of the ion gun 38 is the same asthat of the second embodiment, explanation thereof is omitted.

Hereafter, an example of the method for depositing a film using the filmdeposition system 1 a will be explained.

In this embodiment, a case where metallic silicon (Si) as the first filmdeposition material is used as the targets 82 a and 82 b, and the secondfilm deposition material as a material for coating the oil-repellentfilm is charged in the boat of the evaporation source 36 is exemplified.Further, a case where nitrogen gas is used as the reactive gas isexemplified.

In this embodiment, there is exemplified a case where the first film 103is deposited by the sputtering method, then the first irradiationtreatment (postoperative irradiation) is carried out with an ion beamgenerated by the ion gun for the first film 103, and then theoil-repellent film 105 is further deposited by the vacuum vapordeposition method of resistance heating type.

In the film deposition of the first film 103 by the sputtering method,for example, an intermediate thin film is coated by a sputtering stepfor adhering a thin film having a thickness considerably smaller thanthe objective thickness to the surface of the substrate 101 and areaction step for performing a nitridation treatment of the thin film toconvert the composition of the thin film, and these sputtering step andreaction step are repeated a plurality of times to laminate a pluralityof the intermediate thin layers to coat the first film 103 as a finalthin film having the objective thickness on the surface of the substrate101. Specifically, by repeating a step of coating an intermediate thinfilm having an average thickness of about 0.01 to 1.5 nm determinedafter conversion of the composition on the surface of the substrate 101through the sputtering step and the reaction step, the first film 103 asthe final thin film having an objective thickness of about several toseveral hundreds of nanometers is coated.

(1) First, the substrate 101 is set on the rotary drum 4 outside thevacuum vessel 2, and accommodated in the load lock chamber of the vacuumvessel 2. The substrate 101 is preferably subjected to wet cleaningbefore or after the setting.

Then, the rotary drum 4 is moved to the inside of the vacuum vessel 2along a rail. At the same time, the targets 82 a and 82 b in thesputtering region 80A are held by the sputtering electrodes 81 a and 81b, respectively. Then, the inside of the vacuum vessel 2 is sealed, andthe inside of the vacuum vessel 2 is decompressed to a predeterminedpressure by using the vacuum pump 15 a.

(2) Then, by driving the motor 40 provided behind the vacuum vessel 2,rotation of the rotary drum 4 is started. The revolving speed (RS) ofthe rotary drum 4 is selected to be, for example, 25 rpm or higher,preferably 30 rpm or higher, more preferably 50 rpm or higher. If thevalue of RS is made unduly small, there arises a tendency that thesputtering time for one sheet of the substrate 101 becomes longer, as aresult, the thickness of the thin film coated on the substrate 101becomes thicker, and thus the plasma treatment in the plasma treatmentregion 60A cannot be sufficiently performed. On the other hand, if thevalue of RS is made unduly large, the sputtering time for one sheet ofthe substrate 101 becomes shorter, the number of particles deposited oneach substrate 101 decreases to make the thickness of the thin filmunduly thin, and thus production efficiency may be affected. For thisreason, the value of RS is preferably 250 rpm, more preferably 200 rpm,still more preferably 100 rpm, at most.(3) Then, electric power is supplied to the sputtering electrodes 81 aand 81 b from the AC power supply 84 in a state that argon gas isintroduced into the sputtering region 80A from the sputtering gasfeeding means 90 to carry out the sputtering of the targets 82 a and 82b. Flow rate of the argon gas is appropriately set to be in the range ofabout 250 to 1000 sccm. In this state, the rotary drum 4 is rotated totransfer the substrate 101 to the sputtering region 80A, and coatdeposit (microfilm) of metallic silicon (Si) on the surface of thesubstrate 101. For this deposition, heating of the substrate 101 is notrequired (room temperature). However, the substrate 101 may be heated toa temperature as low as, for example, 220° C. or lower, preferably 150°C. or lower, more preferably 100° C. or lower, still more preferably 80°C. or lower, and preferably about 50° C. or higher.(4) Then, an alternating voltage is applied to the antenna 63 from theradio frequency power supply 65 in a state that nitrogen gas isintroduced into the inside of the plasma treatment region 60A from thereactive gas supply means 70 to generate plasma of nitrogen gas in theplasma treatment region 60A. In this state, the rotary drum 4 is rotatedto transfer the substrate 101 to the plasma treatment region 60A. Insidethe plasma treatment region 60A, plasma of nitrogen gas is generated,and therefore 3 moles of metallic silicon Si adhering to the surface ofthe substrate 101 reacts with 2 moles of nitrogen gas to coat 1 mole ofsilicon nitride (Si₃N₄), which constitute the intermediate thin film. Inaddition, heating of the substrate 101 is not particularly required alsoin this step (room temperature).

Time of this step is appropriately chosen to be within the range of, forexample, about 1 to 60 minutes. Flow rate of the nitrogen gas is alsoappropriately chosen to be about 70 to 500 sccm, and the electric powersupplied from the radio frequency power supply 65 is also appropriatelydetermined to be within the range of about 1.0 to 5.0 kW. Pressure ofthe nitrogen gas introduced into the plasma treatment region 60A (filmdeposition pressure) is preferably about 0.3 to 0.6 Pa. The flow rate ofthe nitrogen gas can be controlled with the massflow controller 72, andthe electric power supplied from the radio frequency power supply 65 canbe controlled with the matching box 64.

In this embodiment, the rotary drum 4 is continuously rotated tosuccessively repeat the sputtering treatment and the plasma treatment tolaminate a plurality of intermediate thin films and thereby coat thefirst film 103 that consists of an Si₃N₄ thin film having a desiredthickness (first film deposition process).

In addition, in this embodiment, it is also preferable to subject thesubstrate 101 to a pretreatment by the plasma treatment described in (4)mentioned above in advance of the first film deposition process. Thispretreatment may be performed for a short time of, for example, about 1to 10 minutes.

(5) Then, after the operations in the sputtering region 80A and theplasma treatment region 60A are terminated, the irradiation electricpower for the ion gun 38 is increased from that of the idling state to apredetermined irradiation electric power, and the shutter 38 a is openedto start irradiation of an ion beam on the first film 103. This step isan example of the first irradiation treatment (postoperativeirradiation). This embodiment is also characterized in that thepostoperative irradiation is performed for the first film 103 coated onthe surface of the substrate 101. The postoperative irradiation can beperformed with the same conditions as those explained for the secondembodiment.(6) Then, the irradiation electric power for the ion gun 38 is returnedto the level of the idling state, the shutter 38 a is closed, and theshutter 36 a is opened to start the operation in the vapor depositionregion 30A. Specifically, the second film deposition material as amaterial for coating the oil-repellent film charged in the crucible(boat) 36 b is heated. And the inside of the vacuum vessel 2 is sealed,and the inside of the vacuum vessel 2 is decompressed to a predeterminedpressure using the vacuum pump 15 a.(7) Then, as in the case of (2) mentioned above, by driving the motor 40provided behind the vacuum vessel 2, rotation of the rotary drum 4 isstarted. The rotary drum 4 is rotated at a revolving speed (RS) similarto that used in (2) mentioned above.

If the shutter 36 a is opened, the heated second film depositionmaterial diffuses into the vapor deposition region 30A, and a part of itadheres to the surface of the first film 103 of the substrate 101subjected to the postoperative irradiation and held by the rotary drum 4under rotation, so that deposition of a film having a predeterminedthickness is attained (second film deposition process). In thisembodiment, film deposition rate of the second film deposition materialis, for example, 0.1 nm/second or higher, preferably 0.2 to 0.4nm/second.

As a result, the oil-repellent film 105 is deposited with apredetermined thickness on the first film 103 subjected to thepostoperative irradiation. By performing the steps described above, theoil-repellent substrate 100 shown in FIG. 1 is produced.

The method for depositing a film using the film deposition system 1 aaccording to this embodiment also exhibits the same effects as thoseobtained by the second embodiment.

In this embodiment, an example of coating only the Si₃N₄ thin film asthe first film 103 on the substrate 101 is explained. However, togetherwith this Si₃N₄ thin film, another thin film such as SiO₂ thin film andAl₂O₃ thin film can also be laminated. In such a case, what is necessaryis to appropriately change materials of the targets 82 a and 82 b of thesputtering means 80 disposed in the sputtering region 80A. Further, asthe first film 103 coated on the substrate 101, a thin film other thanSi₃N₄ thin film, for example, an SiO₂ thin film or Al₂O₃ thin film maybe coated instead of the Si₃N₄ thin film. In such a case, what isnecessary is to appropriately change the materials of the targets 82 aand 82 b to any of various metals such as Al, Zr and Cr, or a pluralityof kinds of metals, or to change type of the reactive gas to, forexample, oxygen gas, fluorine gas, ozone gas, or the like.

Further, in this embodiment, a second irradiation treatment(preoperative irradiation) similar to that of the second embodiment canalso be performed for the substrate 101 in advance of the first filmdeposition process. The preoperative irradiation also includes theplasma treatment described in (4) mentioned above.

In addition, in the explained example of this embodiment, the ion gun 38is disposed at a lower part of the vacuum vessel 2 in the verticaldirection. However, disposition of the ion gun 38 is not essential. Ifthe ion gun 38 is not disposed, it is preferable to dispose a mechanismfor positively applying a bias voltage to the rotary drum 4 as asubstrate holding mechanism. If a bias voltage is applied to the rotarydrum 4, directivity is imparted to the ions in the thermal plasmagenerated by the plasma generation means 60 by the bias voltage. If suchions imparted with directivity collide with the surface of the firstfilm 103 coated in (3) and (4) mentioned above under appropriateconditions, appropriate unevenness is imparted to the first film 103.

EXAMPLES

Hereafter, the present invention will be explained in detail withreference to examples, which more specifically embodies theaforementioned embodiments of the present invention.

Example 1

In this example, a film deposition system having the configuration ofthe film deposition system 1 shown in FIG. 2 for performing ionbeam-assisted vapor deposition was prepared, and oil-repellent substratesamples were obtained by film deposition performed under the conditionsshown in Table 1A, 1B, 1C and 1D.

As the substrate 101, a glass substrate having a pencil hardness of 6Hwas used. The “hardness” used here is a value of the pencil hardnessmeasured by the method defined in JIS-K5600-5-4.

The substrate 101 was subjected to wet cleaning before film deposition.

SiO₂ was used as the first film deposition material, and only forExperimental Examples 1-1 and 1-2, in advance of the ion beam-assistedvapor deposition (first film deposition process) with this first filmdeposition material, the surface of the substrate 101 was subjected toion cleaning using the ion gun 38 for a predetermined time (10 minutesand 5 minutes) (preoperative irradiation, number of irradiated ions:1.1×10¹⁷ ions/cm² in the case of 10 minutes, 5.6×10¹⁶ ions/cm² in thecase of 5 minutes).

Conditions of the ion cleaning were as follows: accelerating voltage:1000 V, electric current: 30 μA/cm², type and introduced volume ofintroduced gas: O₂ at 30 sccm+Ar at 20 sccm).

Substrate temperature at the time of the first film deposition processwas 150° C. Operation conditions of the neutralizer except forExperimental Example 2 were as follows: accelerating voltage: 30 to 70V, electronic current: 1 A, type of introduced gas: (O₂+Ar), andintroduced volume of gas: 50 sccm. The values of hardness of the SiO₂thin films observed before and after the first irradiation treatment(postoperative irradiation) are values of pencil hardness measured bythe method described above. The values of the “center line averageheight (Ra)”, “10-point average height (Rz)”, and “maximum valley depth(Pv)” of the SiO₂ thin films observed after the postoperativeirradiation are values measured according to JIS-B0601. The values of“convex cycle” of the SiO₂ thin films observed after the postoperativeirradiation are values measured with an atomic force microscope (AFM,trade name: SPI-3700, Seiko Instruments Inc.). As the second filmdeposition material, an oil repellent agent produced by Canon. Optron,Inc. (trade name: OF-SR, component: fluorine-containing organosiliconcompound) was used.

TABLE 1 First film deposition process (electron beam-assisteddeposition) Preoperative irradiation (ion cleaning) Ion assistanceconditions Accel- Introduced gas Number Accel- Experi- erating CurrentIntro- of irradi- erating Current Introduced gas mental volt- densityduced Time ated ions voltage density Introduced Exam- age (μA/ volume(sec- (ions/ V1 I1 volume ple (V) cm²) Type (sccm) ond) cm²) (V)(μA/cm²) Type (sccm) 1 — — — — — — 1000 30 O₂ 40 1-1 1000 30 Ar + O₂20 + 30 600 1.1E+17 1000 30 O₂ 40 1-2 1000 30 Ar + O₂ 20 + 30 3005.6E+16 1000 30 O₂ 40 2 — — — — — — — — — — 3 — — — — — — 1000 30 O₂ 404 — — — — — — 800 30 O₂ 40 5 — — — — — — 800 30 O₂ 40 6 — — — — — — 100030 O₂ 40 7 — — — — — — 1000 30 O₂ 40 8 — — — — — — 1000 60 O₂ 40 9 — — —— — — 1000 120 O₂ 40 First film deposition process (electron beam-assisted deposition) First irradiation treatment (irradiation of energyparticles) Experi- Depo- Accel- Current Introduced gas Number of mentalsition SiO₂ thin film erating density Introduced irradiated Exam- rate(nm/ Thickness Hard- voltage I2 volume Time T2 particles ple second)(nm) ness V2 (V) (μA/cm²) Type (sccm) (second) (particles/cm²) 1 0.12515 9 H 1000 30 Ar 40 20 3.7E+15 1-1 0.125 15 9 H 1000 30 Ar 40 203.7E+15 1-2 0.125 15 9 H 1000 30 Ar 40 20 3.7E+15 2 0.25 15 6 H — — — —— — 3 0.125 15 9 H — — — — — — 4 0.125 5 9 H 300 30 Ar 40 20 3.7E+15 50.125 15 9 H 1200 30 Ar 40 20 3.7E+15 6 0.125 10 9 H 1000 10 Ar 40 201.2E+15 7 0.125 15 9 H 1000 60 Ar 40 20 7.5E+15 8 0.25 10 9 H 1000 30 Ar40 4 7.5E+14 9 1 30 9 H 1000 30 Ar 40 100 1.9E+16 Second film depositionFirst irradiation treatment process (vapor deposition Maximum(irradiation of energy particles) by resistance heating) number Experi-SiO₂ thin film Depo- of times of mental Convex Thick- sition Thick-reciprocating Exam- Ra Rz Pv cycle ness rate (nm/ ness cycles in ple(nm) (nm) (nm) (nm) (nm) Material minute) (nm) scratching test 1 5 17 3122 10 OF-SR 0.5 4 2400 1-1 5 17 31 22 10 OF-SR 0.5 4 2500 1-2 5 17 31 2210 OF-SR 0.5 4 1700 2 3 5 30 3 15 OF-SR 0.5 4 400 3 1 3 30 5 15 OF-SR0.5 4 200 4 4 9 19 45 3 OF-SR 0.5 4 1200 5 7 21 43 31 8 OF-SR 0.5 4 25006 3 9 13 21 8 OF-SR 0.5 4 2200 7 9 38 74 57 5 OF-SR 0.5 4 1700 8 2 7 1239 8 OF-SR 0.5 4 2200 9 13 38 134 61 5 OF-SR 0.5 4 1500

Example 2

In this example, a film deposition system having the configuration ofthe film deposition system 1 a shown in FIGS. 3 to 6 for performingmagnetron sputtering was prepared, and oil-repellent substrate sampleswere obtained by film deposition performed under the conditions shown inTable 2A, 2B, and 2C.

As the substrate 101, a glass substrate having a pencil hardness of 6Hwas used. The “hardness” used here is a value of the pencil hardnessmeasured by the method defined in JIS-K5600-5-4.

The substrate 101 was subjected to wet cleaning before film deposition.

As the targets 82 a and 82 b, tabular metallic silicon (Si) targets wereused, and in advance of the first film deposition process, the surfaceof the substrate 101 was subjected to a pretreatment by a plasmatreatment for 1 minute.

Revolving speed (RS) of the rotary drum 4 was 100 rpm. Substratetemperature at the time of the first film deposition process was 100° C.

The values of hardness of Si₃N₄ observed before and after the firstirradiation treatment (postoperative irradiation) are values of pencilhardness measured by the aforementioned method in terms of hardness fora thickness of 100 nm. The values of Ra, Rz and Pv of the Si₃N₄ thinfilms observed after the postoperative irradiation are values measuredaccording to JIS-B0601. The values of “convex cycle” of the Si₃N₄ thinfilms observed after the postoperative irradiation are values measuredwith an atomic force microscope (AFM, trade name: SPI-3700, SeikoInstruments Inc.). As the second film deposition material, an oilrepellent agent produced by Canon Optron, Inc. (trade name: OF-SR,component: fluorine-containing organosilicon compound) was used.

TABLE 2 First film deposition process (sputtering treatment and reactiontreatment) Sputtering Region Plasma treatment region Introduced gasIntroduced gas Experi- Applied Intro- Applied AC Intro- Si₂N₄ thin filmmental electric duced Deposition electric voltage duced Thick- Exam-power volume rate (nm/ power Frequency volume ness Hard- ple (kW) Type(sccm) second) (kW) (MHz) Type (sccm) (nm) Ness 10 5 Ar 100 0.25 1 13.56N₂ 100 10 9 H 11 First irradiation treatment (irradiation of energyparticles) Introduced gas Exper- Accel- Current Intro- Time Number ofSi₂N₄ thin film imental erating Density duced T2 irradiated ConvexThick- Exam- Voltage I2 volume (sec- particles Ra Rz Pv cylcle ness pleV2 (V) (μA/cm²) Type (sccm) ond) (particles/cm²) (nm) (nm) (nm) (nm)(nm) 10 1000 30 Ar 50 20 3.75E+15 5 14 41 25 7 11 — — — — — — 2 4 19 410 Second film deposition process Maximum number (vapor deposition byresistance heating) of times of Experimental Deposition rate Thicknessreciprocating cycles Example Material (nm/minute) (nm) in scratchingtest 10 OF-SR 0.5 4 2800 11 OF-SR 0.5 4 500

Evaluation

A scratching test was performed by placing steel wool #0000 of 1 cm² onthe surface of the oil-repellent film 105 of each of the obtainedoil-repellent substrate samples, and reciprocally moving the steel woolalong a straight line of 50 mm at a speed of 1 second for onereciprocating cycle with a load of 1 kg/cm². After every 500 times ofthe reciprocating cycles of the scratching test, lines were drawn on thetest surface (surface of the oil-repellent film 105) with an oily marker(organic solvent type marker, trade name: Mckee Extra Fine, Zebra Co.,Ltd.), and it was evaluated whether the organic solvent type ink of theorganic solvent type marker could be wiped off with dry cloth. As aresult, the maximum numbers of times of the reciprocating cyclesallowing wiping off of the organic solvent type ink were as shown inTable 1A, 1B, 1C and 1D and Table 2A, 2B, and 2C mentioned above.

Discussion

From the results shown in Table 1A, 1B, 1C and 1D, superior usefulnessof the samples of Experimental Examples 1, 1-1 and 1-2 could beconfirmed compared with the samples of Experimental Examples 2 and 3. Inparticular, it could be confirmed that the maximum number of times ofthe reciprocating cycles in the scratching test could be increased byperforming ion cleaning (preoperative irradiation) for the surface ofthe substrate 101 for a predetermined time in advance of the first filmdeposition process (ion beam-assisted) (Experimental Example 1-1)compared with the case where ion cleaning was not performed(Experimental Example 1). In addition, it could be confirmed that, whenthe time of the preoperative irradiation was shortened from 10 minutesto 5 minutes, the maximum number of times of the reciprocating cycles inthe scratching test was decreased, but sufficient maximum number oftimes of the reciprocating cycles in the scratching test could be stillobtained compared with the results of Experimental Examples 2 and 3.

Further, it could also be confirmed that even if the conditions of theirradiation of energy particles were changed, evaluation resultssubstantially the same as those of Experimental Example 1 could beobtained (Experimental Examples 2 to 7).

From the results shown in Table 2A, 2B, and 2C, superior usefulness ofthe sample of Experimental Example 10 could be confirmed compared withthe sample of Experimental Example 11.

The reason why the organic solvent type ink of the oily marker could bewiped off with dry cloth even after the number of times of thereciprocating cycles in the scratching test exceeded 500 for the samplesof Experimental Examples 1, 1-1, 1-2 and 4 to 10 as shown in Table 1A,1B, 1C and 1D is not necessarily clear. However, it is estimated asfollows. That is, appropriate convexes and concaves are imparted to thesurface of the first film 103 (SiO₂ thin film or Si₃N₄ thin film) havinghardness higher than that of the substrate 101 by the irradiation ofenergy particles (postoperative irradiation). Thus, it is consideredthat, among the convexes and concaves imparted to the first film 103,the convexes secured abrasion resistance, the concaves held thecomponents of the oil-repellent film 105 therein to secure oilrepellency of the sample surfaces, and thereby abrasion resistance ofpractically sufficient level was imparted.

The invention claimed is:
 1. A method for preparing an abrasionresistant oil-repellent film on a substrate comprising: depositing afirst film on a surface of the substrate by a dry ion-assisteddeposition method by simultaneously depositing the first film made of aninorganic material selected from the group consisting of SiO₂, ZrO₂,Si₃N₄ and Al₂O₃, with ion beam exposure, on the substrate to form is thefirst film to a predetermined thickness, with the depositing stoppedwhen the predetermined thickness is formed; and the ion-beam exposurecontinues as a first irradiation treatment to form a roughened surfaceon the first film with a centerline average roughness (Ra): 0.1 to 1000nm, a 10 point average height (Rz): 5 to 2000 nm and a maximum valleydepth (Pv): is 15 to 200 nm, a cycle of projections: 1 to 50 nm; anddepositing a second film having oil repellency on the roughened surfaceby vacuum vapor deposition to form the abrasion resistant oil-repellentfilm on the substrate.
 2. The method for depositing a film according toclaim 1, wherein: the first irradiation treatment uses an ion beam, withions having energy that are irradiated onto the first film, have anaccelerating voltage between 100 and 2000V.
 3. The method for depositinga film according to claim 1, wherein: the first irradiation treatmentuses an ion beam, with ions having energy that are irradiated onto thefirst film, have a current density between 1 and 120 ρA/cm².
 4. Themethod for depositing a film according to claim 1, wherein: the firstirradiation treatment uses an ion beam, with ions having energy areirradiated onto the first film for 1 to 800 seconds.
 5. The method fordepositing a film according to claim 1, wherein the first irradiationtreatment uses an ion beam, with ions having energy are irradiated by anion dose of 1×10¹³ to 5×10¹⁷ ions/cm² onto the first film.
 6. The methodfor depositing a film according to claim 1, wherein: the firstirradiation treatment uses an ion beam, with ions having energy consistof an ion beam containing at least argon.
 7. The method for depositing afilm according to claim 1, wherein: the first film deposited on thesurface of the substrate has the predetermined thickness of 3 to 1000nm.
 8. The method for depositing a film according to claim 1, wherein:an ion being used for the ion beam exposure during depositing the firstfilm, and the ion beam has an accelerating voltage between 100 and 2000V.
 9. The method for depositing a film according to claim 1, wherein: anion being used for the ion beam exposure during depositing the firstfilm, and the ion beam has a current density between 1 and 120 ρA/cm².10. The method for depositing a film according to claim 1, wherein: anion being used for the ion beam exposure during depositing the firstfilm, and the ion beam is irradiated for 1 to 800 seconds.
 11. Themethod for depositing a film according to claim 1, wherein: an ion beingused for the ion beam exposure during depositing the first film, and theion beam is irradiated by an ion dose of 1×10¹³ ions/cm² to 5×10¹⁷ions/cm².
 12. The method for depositing a film according to claim 1,wherein: an ion being used for the ion beam exposure during depositingthe first film is an ion beam of oxygen, argon or a mixed gas of oxygenand argon.
 13. The method for depositing a film according to claim 1,wherein: the first film deposited on the surface of the substrate has ahardness higher than that of the substrate.
 14. The method fordepositing a film according to claim 1, wherein: ions having energy areirradiated to the surface of the substrate prior to deposition of thefirst film.
 15. The method for depositing a film according to claim 1,wherein the substrate is a glass substrate with a pencil hardness of 6Hand the second film is formed from a fluorine-containing organosiliconcompound.